α-一溴代芳杂环乙酮论文：α-溴代芳(杂)环乙酮与取代哌啶的C-N亲核取代反应

-一溴代芳杂环乙酮论文：-溴代芳（杂）环乙酮与取代哌啶的C-N亲核取代反应【中文摘要】芳杂环化合物是重要的医药、农药等精细化工产品的中间体,特别在制药领域有着广泛的应用,因而构建功能结构的哌啶化合物已经引起了人们的广泛关注。基于这样的背景,本论文主要以-溴代芳杂环乙酮和取代哌啶盐酸盐为底物,经C-N亲核取代反应制备新型芳杂环乙酰基取代的哌啶类化合物。实验首先用溴代试剂过溴四丁基溴化铵合成-一溴代芳杂环乙酮;其次根据文献经过C-O亲核取代合成取代哌啶的盐酸盐。然后以这两种新制备的中间体作为反应底物,经C-N亲核取代反应合成具有广泛药用价值的芳杂环乙酰基取代的哌啶类化合物。实验中,考查了不同的原料配比、碱、溶剂和温度对反应的影响,得到较优的反应条件,并在较优的反应条件下,改变原料的取代基进行反应,合成1-2-(2-噻吩基)乙酮等10种双取代的哌啶类衍生物,并通过NMR,MS和IR对目标产物结构进行了表征。【英文摘要】Aromatic heterocyclic compounds are a class of important fine chemical intermediates for the medicines and agricultural chemicals, and were especially applied widely in the pharmaceutical field. Accordingly, great attention has been paid to the construction of functionalized piperidine compounds. Herein, the C-N nucleophilic substitution reaction was carried out using-bromo-aromatic heteroethanone and substituted piperidine as the substrate. First, 2-bromo-1-(thiophen-2-yl)ethanone was synthesized by bromination of aromatic heteroethanone using tetrabutylammo- nium tribromides as brominating agent. Secondly according to the literature,the replaced piperidine hydrochloride was synthesised by the C-O nucleophilic substitution. And then, with the two new preparation intermediates as a reaction to the substrate, the C-N nucleophilic substitution reaction of-bromo-aromatic hetero- ethanone and substituted piperidine to offer the corresponding piperidine derivatives. In this experiment, molar ratio, base, solvent and temperature was investigated to establish the optimum reaction conditions. The 2-4-(Benzothiazol-2-yloxy)-piperidin-1-yl-1- thiophen-2-yl-ethanone etc 10 species double replaced piperidine kind of derivatives were obtained in yield of 73.7% under optimized condition. The structure of the target product was characterized by MS, NMR, and IR.【关键词】-一溴代芳杂环乙酮 C-O亲核取代反应 哌啶 C-N亲核取代反应【英文关键词】-bromo heterocyclic ethanone the C-O nucleophilic substitution reaction piperidine the C-N nucleophilic substitution reaction【备注】索购全文在线加好友：1.3.9.9.3.8848 同时提供论文写作一对一指导和论文发表委托服务【目录】-溴代芳（杂）环乙酮与取代哌啶的C-N亲核取代反应中文摘要4-5ABSTRACT5-61. 文献综述10-381.1 含溴化合物与溴代反应的应用及发展10-151.1.1 芳杂环乙酮的-一溴代化合物的应用11-121.1.2 芳杂环乙酮的溴代方法简介12-151.2 哌啶及其衍生物的应用及发展15-211.2.1 哌啶衍生物在医药上的应用与发展16-171.2.2 哌啶衍生物在农药上的应用与发展17-181.2.3 哌啶衍生物在光稳定剂上的应用与发展181.2.4 双取代哌啶衍生物的应用与发展18-211.3 芳基或芳氧基哌啶的合成21-261.3.1 催化加氢法211.3.2 环化法21-231.3.3 偶联法23-241.3.4 经典合成法24-261.4 氨基保护以及脱 Boc 方法26-301.4.1 常用的氨基保护基26-271.4.2 N-Boc 保护基的脱除方法27-301.5 C-O 和 C-N 偶联反应30-361.5.1 Ullmann 反应30-311.5.2 Ullmann 反应机理311.5.3 Ullmann 反应研究进展31-321.5.4 C-O 键的构建32-341.5.5 C-N 键的构建34-361.6 课题意义36-382. 实验部分38-532.1 原料与试剂382.2 溶剂的处理38-392.3 仪器装置392.4 溴代试剂的制备392.5 -一溴代芳杂环乙酮化合物的制备39-412.5.1 -一溴代噻吩乙酮的制备39-402.5.2 -一溴代呋喃乙酮的制备40-412.5.3 -一溴代对溴苯乙酮的制备412.6 取代哌啶盐酸盐化合物的制备41-452.6.1 2-(4-哌啶氧基)苯并噻唑盐酸盐的制备41-422.6.2 2-(4-哌啶氧甲基)苯并噻唑盐酸盐的制备42-432.6.3 2-(3-哌啶氨基)苯并噻唑盐酸盐的制备43-442.6.4 2-(2-哌啶氧甲基)吡嗪盐酸盐的制备44-452.7 -一溴代芳杂环乙酮与取代哌啶的 C-N 亲核取代反应45-532.7.1 1-4-(2-苯并噻唑氧基)-1-哌啶基-2-(2-噻吩基)乙酮452.7.2 1-4-(2-苯并噻唑氧甲基)-1-哌啶基-2-(2-噻吩基)乙酮45-462.7.3 1-3-(2-苯并噻唑氨基)-1-哌啶基-2-(2-噻吩基)乙酮46-472.7.4 1-2-(2-吡嗪氧甲基)-1-哌啶基-2-(2-噻吩基)乙酮47-482.7.5 1-4-(2-苯并噻唑氧基)-1-哌啶基-2-(2-呋喃基)乙酮482.7.6 1-4-(2-苯并噻唑氧甲基)-1-哌啶基-2-(2-呋喃基)乙酮48-492.7.7 1-3-(2-苯并噻唑氨基)-1-哌啶基-2-(2-呋喃基)乙酮49-502.7.8 1-2-(2-吡嗪氧甲基)-1-哌啶基-2-(2-呋喃基)乙酮50-512.7.9 1-3-(2-苯并噻唑氨基)-1-哌啶基-2-(2-对溴苯基)乙酮512.7.10 1-2-(2-吡嗪氧甲基)-1-哌啶基-2-(2-对溴苯基)乙酮51-533. 结果与讨论53-593.1 芳杂环乙酮一溴代反应的结果533.2 C-O 亲核取代反应及脱 Boc